Copper metallurgy in integrated circuits

ABSTRACT

A typical integrated circuit interconnects millions of microscopic transistors and resistors with aluminum wires buried in silicon-dioxide insulation. Yet, aluminum wires and silicon-dioxide insulation are less attractive than copper wires and polymer-based insulation, which promise both lower electrical resistance and capacitance and thus faster, more efficient circuits. Unfortunately, current techniques cannot realize the promise because copper reacts with the polymer-based insulation to form copper dioxide within the polymer, reducing effectiveness of the copper-polymer combination. Accordingly, the inventor devised a method which uses a non-acid-precursor to form a polymeric layer and then cures, or bakes, it in a non-oxidizing atmosphere, thereby making the layer resistant to copper-dioxidizing reactions. Afterward, the method applies a copper-adhesion material, such as zirconium, to the layer to promote adhesion with a subsequent copper layer. With reduced copper-dioxide, the resulting interconnective structure facilitates integrated circuits with better speed and efficiency.

FIELD OF INVENTION

[0001] The present invention concerns methods of fabricating integrated circuits, particularly methods of forming interconnects from copper and other metals.

BACKGROUND OF THE INVENTION

[0002] Integrated circuits, the key components in thousands of electronic and computer products, are interconnected networks of electrical components fabricated on a common foundation, or substrate. Fabricators typically use various techniques, such as layering, doping, masking, and etching, to build thousands and even millions of microscopic resistors, transistors, and other electrical components on a silicon substrate, known as a wafer. The components are then wired, or interconnected, together to define a specific electric circuit, such as a computer memory.

[0003] Interconnecting millions of microscopic components typically entails covering the components with an insulative layer of silicon dioxide, etching small holes in the insulative layer to expose portions of the components underneath, and digging trenches in the layer to define a wiring pattern. Then, through metallization, the holes and trenches are filled typically with aluminum, to form line-like aluminum wires between the components. The aluminum wires are typically about one micron thick, or about 100 times thinner than a human hair.

[0004] Silicon dioxide and aluminum are the most common insulative and conductive materials used to form interconnections today. However, at sub-micron dimensions, that is, dimensions appreciable less than one micron, aluminum and silicon-dioxide interconnection systems present higher electrical resistances and capacitances which waste power and slow down integrated circuits. Moreover, at these smaller dimensions, aluminum exhibits poor electromigration resistance, a phenomenon which promotes disintegration of the aluminum wires at certain current levels. This ultimately undermines reliability, not only because disintegrating wires eventually break electrical connections but also because aluminum diffuses through surrounding silcon-dioxide insulation to form short circuits with neighboring wires. Thus, at submicon dimensions, aluminum and silicon-dioxide interconnection systems waste power, slow down integrated circuits, and compromise reliability.

[0005] Copper appears, because of its lower electrical resistivity and higher electromigration resistance to be a promising substitute for aluminum. And, many polymers, for example, fluorinated polyimides, because of their lower dielectric constants, appear to be promising substitutes for silicon dioxide. Thus, a marriage of copper with these polymers promises to yield low-resistance, low-capacitance interconnective structures that will improve the efficiency and speed of integrated circuits.

[0006] Unfortunately, copper reacts with these polymers to form conductive copper dioxide within these polymers, reducing their effectiveness as low-capacitance insulators and ultimately leaving the copper-polymer promise of superior efficiency and speed unfulfilled.

SUMMARY OF THE INVENTION

[0007] To address these and other needs, the inventor has developed methods of making copper-polymer interconnection systems with reduced copper oxide. Specifically, one method uses a non-acid-based polymeric precursor, such as ester, instead of the typical acid precursor, to form a polymeric layer, and then cures the layer in a reducing or non-oxidizing atmosphere, thereby making the layer resistant to oxidation. Afterward, a zirconium, hafnium, or titanium layer is formed on the polymeric layer to promote adhesion with a subsequent copper layer. With the reduced formation of copper oxide, the method yields faster and more efficient copper-polymer interconnects.

[0008] Moreover, reducing copper-dioxidation facilitates micron and sub-micron spacing of polymer-insulated copper conductors, which would otherwise require spacings of 10 or more microns. Accordingly, another aspect of the invention is an integrated circuit including at least two conductors which are separated by no more than about one micron of a polymeric insulator. Thus, the inventor provides a method that not only yields copper-polymer interconnects of superior speed and efficiency, but also yields integrated circuits with unprecedented spacing of copper-polymer interconnects.

BRIEF DESCRIPTION OF THE DRAWINGS

[0009] The invention is described with reference to the following figures, wherein like numerals refer to like features:

[0010]FIG. 1 is a cross-sectional view of an integrated-circuit assembly at an early fabrication stage, including transistors 14 a and 14 b, an insulative layer 16, contacts 16 a and 16 b, and a silicon nitride layer 17;

[0011]FIG. 2 is a cross-sectional view of the FIG. 1 integrated-circuit assembly after formation of a polymeric layer 18 over contacts 16 a and 16 b and layer 17 and after formation of a trench 20;

[0012]FIG. 3 is a top view of the FIG. 2 integrated-circuit assembly, showing position of the trench relative contacts 16 a and 16 b;

[0013]FIG. 4 is another cross-sectional view of the FIG. 3 integrated-circuit assembly, taken along line 4-4 to show depth and width of the trench;

[0014]FIG. 5 is a cross-sectional view of the FIG. 4 assembly after formation of a copper-adhesion layer 22 and a copper layer 24;

[0015]FIG. 6 is a cross-sectional view of the FIG. 5 assembly after removal of excess portions of layers 22 and 24 leaves copper conductor 24′;

[0016]FIG. 7 is a cross-sectional view of the FIG. 6 assembly taken along line 7-7 after formation of another polymeric layer 26 having a via hole 28;

[0017]FIG. 8 is a top view of the FIG. 7 assembly, showing position of the via hole relative conductor 24′;

[0018]FIG. 9 is a cross-sectional view of the FIG. 8 assembly after formation of a copper-adhesion layer 30 and copper contact 32;

[0019]FIG. 10 is a cross-sectional view of an integrated-circuit assembly having two copper conductors 24 a′ and 24 b′ in a polymeric insulator 18, with the conductors separated by no more than about one micron; and

[0020]FIG. 11 is a block diagram of an integrated memory circuit which incorporates the present invention.

DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS

[0021] The following detailed description, which references and incorporates FIGS. 1-11, describes and illustrates one or more specific embodiments of the invention. These embodiments, offered not to limit but only to exemplify and teach the invention, are shown and described in sufficient detail to enable those skilled in the art to practice the invention. Thus, where appropriate to avoid obscuring the invention, the description may omit certain information known to those of skill in the art.

[0022] FIGS. 1-9 show a number of exemplary integrated-circuit assemblies, which taken collectively and sequentially, illustrate an exemplary method of the present invention. The method, as shown in FIG. 1, a cross-sectional view, begins with a known integrated-circuit assembly or structure 11, which can be within any integrated circuit, an integrated memory circuit, for example. Assembly 11 includes a substrate 12. The term “substrate,” as used herein, encompasses a semiconductor wafer as well as structures having one or more insulative, semi-insulative, conductive, or semiconductive layers and materials. Thus, for example, the term embraces silicon-on-insulator, silicon-on-sapphire, and other advanced structures.

[0023] Substrate 12 supports a number of integrated elements 14, such as transistors 14 a and 14 b. Transistors 14 a and 14 b are covered by a 100-nanometer-thick, insulative layer 16, which, for example, comprises a silicon oxide. A silicon-nitride layer 17, also 100-nanometers thick, covers layer 16. Extending through layers 16 and 17 are two tungsten vias (or contact plugs) 16 a and 16 b electrically connected to respective transistors 14 a and 14 b. Although omitted from FIGS. 1-9 for clarity, assembly 11 preferably includes a titanium-nitride (TiN) diffusion barrier between vias 16 a and 16 b and transistors 14 a and 14 b.

[0024]FIG. 2 shows that the first step of the exemplary method entails forming a polymeric layer 18 atop layer 17. As used herein, the term “polymeric” encompasses organic polymers, organic oligomers, and organic monomers. Collectively, these may be described as materials containing one or more mer units having a carbon-chain backbone. In addition, “polymeric” encompasses materials having properties similar to those of organic polymers. For instance, organic polymers characteristically have high ductility, low elastic modulus, low compressive-yield strength, and/or low thermal-expansion coefficients. Moreover, as used herein, polymeric encompasses polymer precursors, or bases.

[0025] In the exemplary embodiment, polymeric layer 18 begins as a non-acid polymeric precursor, that is, a precursor with a pH greater than about 6. Examples of polymeric precursors include a polyimide ester, such as the type sold by E.I. du Pont de Nemours under the tradename PI-2801, or a polymeric-precursor derivative based on fluorine, bromine, or other elements from the fluorine periodic group. Other embodiments form polymeric layer 18 as a foamed polymer, which will generally have a lower dielectric constant than most non-foamed polymers and thus provides further capacitance reductions. An example of a foamed polymer is taught in co-pending and co-assigned patent application Ser. No. 08/892,114 filed Jul. 14, 1997. This application, entitled Method of Forming Insulating Material for an Integrated Circuit and Integrated Circuits Resulting from Same, is incorporated herein by reference.

[0026] Subsequent to its formation from a non-acid precursor, polymeric layer 18 is cured, with the resultant layer having a thickness of about 500 nanometers. In the exemplary embodiment, the curing procedure has three phases: the first at 125° C. for 15 minutes, the second at 250° C. for 30 minutes, and the third at 375° C. for 30 minutes, with the second and third phases occurring in a non-oxidizing, or reducing, atmosphere to inhibit oxidation. Some exemplary atmospheres are pure hydrogen or mixtures of about 3-to-10% hydrogen with nitrogen, argon, or helium. Starting with the non-acid precursor and curing according to this procedure ultimately reduces the amount of oxidization that occurs in subsequent processing by about four fold. Therefore, unlike conventional polymeric processing, this procedure prevents or reduces increases in the dielectric constant of polymeric layer 18.

[0027] The next step, best illustrated in FIG. 3, a top view of the FIG. 2 assembly, is to define the stud and wiring patterns on layer 18, using for example suitable masking and etching techniques. In the exemplary embodiment, this entails using reactive-ion etching or any selective-material-removal technique to form a trench 20, which will ultimately define a conductor for connecting vias 16 a and 16 b. FIG. 3 shows that trench 20 has ends 20 a and 20 b which correspond with respective vias 16 a and 16 b. FIG. 4, a cross-section of assembly 11 taken along line 4-4 in FIG. 3, shows that trench 20 has a depth 20 d of about 500 nanometers to expose vias 16 a and 16 b, and a width 20 w of about 250 nanometers. Thus, in this exemplary embodiment, trench 20 has an approximate aspect ratio of 2-to-1.

[0028] The next step, shown in FIG. 5, entails applying a 10-nanometer-thick adhesion layer 22 on layer 18, inside and outside trench 20. The principle purpose of the adhesion layer, which may also be called a seed, contact, or cladding layer, is to promote adherence of a copper layer formed in the next step. Examples of suitable adhesion-layer materials include zirconium, hafnium, titanium. Zirconium, however, is preferable to titanium since it has at least a ten-fold lower solubility in copper.

[0029] Next, to form a copper conductor, the method fills trench 20, as FIG. 5 shows, by depositing a 975-nanometer-thick copper layer 24 on layer 22 and inside trench 20. In some embodiments another 10-nanometer-thick adhesion layer is formed atop copper layer 24 to inhibit copper oxidation during later processing, particularly during curing of subsequent polymeric layers. To reduce copper oxidation, one embodiment performs the adhesion-material and the copper deposition at temperatures less than 450° C., another embodiment at temperatures between about 250 and 350° C., and another at around 300° C.

[0030] In the 250-350° C. range, a thin layer of Cu₅Zr (or Beta), tends to initially form at the interface of the copper and zirconium layers, inhibiting diffusion of zirconium into the copper and preventing it from significantly increasing resistance of the copper. A similar effect may be achieved by electroplating the copper and heat-treating the zirconium and copper layers at 250-350° C. for one to two hours, before curing the polymer. Inhibiting the diffusion of zirconium into the copper ultimately yields a copper conductor with a conductivity greater than 95 percent of IACS, or International Annealed Copper Standard. The International Annealed Copper Standard (IACS) is 1.7241 microhm-centimeters at 20 C, or 17.241 nanaohm-meters. Thus, the exemplary copper conductor has a conductivity greater than about 16.4 nanaohm-meters. However, in other embodiments the conductor is in the range of 14 nanohm-meters or greater.

[0031] Afterwards, excess copper and zirconium on the surface are then removed using a chemical-mechanical polishing technique. FIG. 6 shows the resulting metal conductor 24′, which electrically connects vias 16 a and 16 b and therefore connects transistors 14 a and 14 b. Formation of conductor 24′ completes the first level of metallization.

[0032]FIG. 7 shows that the second level metallization starts with formation and curing of a second polymeric layer 28 on layer 22. In some embodiments, layer 28 has a composition similar to polymeric layer 18. Subsequently, the method cures layer 28, again following a three-phase curing procedure with temperatures similar to those used for layer 18. The first phase preferably occurs in hydrogen, high-purity forming gas, or a non-oxidizing high-purity argon, and the second and third phases preferably occur in a non-oxidizing atmosphere of high-purity argon. In contrast to conventional curing procedures, this curing procedure, devised primarily for second and subsequent polymeric layers, takes particular care to avoid inciting reactions with and between existing polymeric and copper structures, for example, layer 18 and conductor 24′. Therefore, this procedure safeguards the dielectric strength of polymeric layer 18.

[0033] After curing polymeric layer 28, the method defines a stud and/or wiring pattern using any suitable technique. The exemplary embodiment defines a vertical stud, or via, hole 28 a in layer 28, using masking and etching techniques. (Hole 28 a may also be viewed as the cross-section of a trench, defining a wire that intersects, or contacts, copper conductor 24′ which lies below.) Other embodiments form hole 28 a along with other wiring trenches similar to trench 20, according to conventional dual-damascene techniques, which fill via holes and trenches in one metallization. FIG. 8 shows the position of hole 28 a relative transistors 14 a and 14 b, vias 16 a and 16 b, and conductor 24′ from the first metallization level.

[0034] The next steps form a 10-nanometer-thick adhesion layer 30, similar to adhesion layer 22, on polymeric layer 28, as well as a copper layer 32 on layer 28. (Other embodiments form an additional adhesion layer on copper layer 32.) Layers 30 and 32, in the exemplary embodiment, are deposited at approximately 300° C. As already noted, depositing zirconium and copper at this temperature tends to form a thin interfacial layer of Cu₅Zr (not shown) between layers 30 and 32, which ultimately enhances conductivity of the resulting conductor. Subsequent annealing also promotes formation of this interfacial layer.

[0035] After completion of layer 32, excess copper and adhesion-layer material are removed, for example, by chemical-mechanical polishing. FIG. 9 shows that the resulting integrated-circuit assembly includes a copper via 34′ electrically connected to underlying conductor 24′ and thus also connected to transistors 14 a and 14 b. Subsequent metallizations would follow similarly.

[0036] In addition to preservation of the dielectric constant of the polymeric layers, the oxidation reductions stemming from the present invention also allow closer spacing of copper conductors in polymeric insulators, particularly micron and sub-micron spacing. FIG. 10, a juxtaposition of two of the assemblies shown in FIG. 6, shows two side-by-side copper structures (for example contact plugs or wires) 24 a′ and 24 b′ separated by a distance 25 which is less than about one micron in one embodiment. In various embodiments, distance 25 is less than about 0.75 microns, less than about 0.5 microns, or less than about 0.25 microns. In contrast, conventional techniques for forming copper-polymer interconnections require intra-polymer conductor spacings of 20 or more microns to maintain isolation of the conductors after uninhibited formation of conductive copper dioxide in the polymer between conductors. Thus, the micron and submicron spacings of the present invention provide a dramatic improvement.

Exemplary Embodiment of an Integrated Memory Circuit Incorporating the Copper-Polymer Interconnection System

[0037]FIG. 11 shows one example of the unlimited number of applications for the copper-polymer interconnections of the present invention: a generic integrated memory circuit 40. Circuit 40, which operates according to well-known and understood principles, is generally coupled to a processor (not shown) to form a computer system. More precisely, circuit 40 includes a memory array 42 which comprises a number of memory cells 43, a column address decoder 44, and a row address decoder 45, bit lines 46, word lines 47, and voltage-sense-amplifier circuit 48 coupled to bit lines 46.

[0038] In the exemplary embodiment, each of the memory cells, the address decoders, and the amplifier circuit includes two or more zirconium-clad copper conductors embedded in polymeric insulation according to the present invention. In addition, connections between the address decoders, the memory array, the amplifier circuit are implemented using similar copper-polymer interconnects. The spacings of these conductors, in some embodiments, follow the micron and submicron spacings noted for FIG. 10.

Conclusion

[0039] The present invention provides a method of forming copper-polymer interconnections systems, which reduces the tendency of polymers to react with copper and form undesirable copper oxides. Formation of these copper oxides would otherwise reduce the effectiveness of the polymers as low-capacitance insulators and thus offset their ability to improve speed and efficiency of integrated circuits. Thus, the present invention ultimately facilitates the fabrication of integrated circuits having superior speed and efficiency. Moreover, because the reduction in oxidation allows closer placement of polymer-insulated copper wires, the invention also facilitates denser integrated circuits, that is, circuits with greater numbers of components in the same space.

[0040] The embodiments described above are intended only to illustrate and teach one or more ways of practicing or implementing the present invention, not to restrict its breadth or scope. The actual scope of the invention, which encompasses all ways of practicing or implementing the invention, is defined only by the following claims and their equivalents. 

1. A method of making copper-polymer-based interconnections in an integrated circuit, the method comprising: forming a non-acid-based polymeric layer in the integrated-circuit assembly; curing the polymeric layer in a non-oxidizing atmosphere; and forming at least one copper structure on the non-acid-based polymeric layer.
 2. The method of claim 1 further comprising applying a copper-adhesion material to the polymeric layer before forming the one copper conductor.
 3. The method of claim 1 wherein forming the non-acid-based polymeric layer comprises applying a non-acid-based polymeric precursor to a layer in the integrated-circuit assembly.
 4. The method of claim 1 wherein forming the non-acid-based polymeric layer comprises applying a polyimide ester to a layer in the integrated-circuit assembly.
 5. The method of claim 1 wherein the polymeric layer comprises a polyimide.
 6. The method of claim 1 wherein forming the one copper structure on the polymeric layer comprises: depositing at least one of zirconium, hafnium, or titanium on the polymeric layer; and depositing copper on the deposited zirconium, hafnium, or titanium.
 7. The method of claim 6 wherein depositing at least one of zirconium, hafnium, or titanium and depositing copper occur within an approximate temperature range of 250 to 350° C.
 8. The method of claim 1 wherein the non-oxidizing atmosphere comprises at least one of hydrogen, nitrogen, or argon.
 9. The method of claim 1 further comprising: forming another non-acid-based polymeric layer over the one copper structure; curing the other non-acid polymeric layer in an argon atmosphere; and forming another copper structure on the other non-acid-based polymeric layer.
 10. The method of claim 1 wherein forming the copper structure occurs after curing the non-acid-based polymeric layer.
 11. A method of making copper-polymer-based interconnections in an integrated circuit, the method comprising: forming a non-acid-based polymeric layer in the integrated-circuit assembly; curing the polymeric layer in a non-oxidizing atmosphere; applying a copper-adhesion material to the polymeric layer; and forming at least one copper structure that contacts the copper-adhesion material on the polymeric layer.
 12. The method of claim I1 wherein forming the non-acid-based polymeric layer comprises applying a polyimide ester to a layer in the integrated-circuit assembly.
 13. The method of claim 11 wherein the polymeric layer comprises a polyimide.
 14. The method of claim 11 wherein forming the one copper structure on the polymeric layer comprises: depositing at least one of zirconium, hafnium, or titanium on the polymeric layer; and depositing copper on the deposited zirconium, hafnium, or titanium.
 15. The method of claim 14 wherein depositing at least one of zirconium, hafnium, or titanium and depositing copper occur within an approximate temperature range of 250 to 350° C.
 16. The method of claim 11 further comprising: forming another non-acid-based polymeric layer over the copper structure; curing the other non-acid precursor in an argon atmosphere; forming another copper structure on the other non-acid-based polymeric layer.
 17. The method of claim 11 wherein forming the copper structure occurs after curing the non-acid-based polymeric layer in a non-oxidizing environment.
 18. A method of making copper-polymer-based interconnections in an integrated circuit, the method comprising: forming an ester-based polyimide layer in the integrated-circuit assembly; curing the polyimide layer in a non-oxidizing atmosphere; applying a copper-adhesion material to the polyimide layer; and forming at least one copper structure that contacts the copper-adhesion material on the polyimide layer.
 19. The method of claim 18 wherein the copper-adhesion material comprises at least one of zirconium, hafnium, or titanium.
 20. The method of claim 18 wherein applying the copper-adhesion material comprises depositing zirconium within an approximate temperature range of 250 to 350° C.
 21. The method of claim 18 wherein forming the one copper structure occurs after curing the ester-based polyimide layer.
 22. A method of making copper-polymer-based interconnections in an integrated circuit, the method comprising: forming a first non-acid-based polymeric layer in the integrated-circuit assembly; forming at least one copper structure on the first non-acid-based polymeric layer; forming a second non-acid-based polymeric layer in the integrated-circuit assembly; curing the second non-acid-based polymeric layer in a non-oxidizing atmosphere; and depositing copper on the second non-acid-based polymeric layer at a temperature less than about 450° C.
 23. The method of claim 22 further comprising applying a copper-adhesion material, comprising at least one of zirconium, titanium, and hafnium, to the second polymeric layer before depositing copper.
 24. The method of claim 22 wherein forming the non-acid-based polymeric layer comprises applying a polyimide ester precursor to a layer in the integrated-circuit assembly.
 25. The method of claim 22 wherein depositing copper occur within an approximate temperature range of 250 to 350° C.
 26. The method of claim 22 wherein the non-oxidizing atmosphere comprises at least one of hydrogen, nitrogen, and argon.
 27. A method of electrically connecting first and second components in an integrated-circuit assembly, the method comprising: forming an ester-based polyimide layer over the first and second components; curing the polyimide layer in a non-oxidizing atmosphere; forming a trench in the polyimide layer, the trench having respective first and second regions overlying the first and second components; depositing a copper-adhesion material in the trench; and at least partially filling the trench with copper.
 28. The method of claim 27 wherein the copper-adhesion material comprises at least one of zirconium, hafnium, or titanium.
 29. The method of claim 27 wherein depositing the copper-adhesion material and depositing the copper occur within an approximate temperature range of 250 to 350° C.
 30. The method of claim 27 wherein forming the one copper structure occurs after curing the ester-based polyimide layer.
 31. An integrated circuit comprising at least two copper structures no more than about one micron apart and a polymeric insulator between the two copper structures.
 32. The integrated circuit of claim 31 wherein at least one of the two copper structures is at least partially clad with zirconium.
 33. An integrated circuit comprising a copper structure at least partially clad with zirconium, with the copper structure having a conductivity which is at least as great as 90 percent of the International Annealed Copper Standard.
 34. An integrated circuit comprising a copper structure with a zirconium cladding and a layer of Cu₅Zr between at least a portion of the copper structure and the zirconium cladding.
 35. An integrated memory circuit comprising at least two copper structures no more than about one micron apart and a polymeric insulator between the two copper structures.
 36. An integrated memory circuit comprising a copper structure at least partially clad with zirconium, with the copper structure having a conductivity which is at least as great as 95 percent of the International Annealed Copper Standard.
 37. An integrated memory circuit comprising a copper structure with a zirconium cladding and a layer of Cu₅Zr between at least a portion of the copper structure and the zirconium cladding.
 38. A system comprising: a processor; and an integrated memory circuit coupled to the processor, with the memory circuit comprising at least two copper structures no more than about one micron apart and a polymeric insulator between the two copper structures.
 39. A system comprising: a processor; and an integrated memory circuit coupled to the processor, with the memory circuit comprising a copper structure at least partially clad with zirconium, with the copper structure having a conductivity which is at least as great as 95 percent of the International Annealed Copper Standard. 